US20190112530A1 - Cooling apparatus for carbonized biomass - Google Patents

Cooling apparatus for carbonized biomass Download PDF

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Publication number
US20190112530A1
US20190112530A1 US16/090,515 US201716090515A US2019112530A1 US 20190112530 A1 US20190112530 A1 US 20190112530A1 US 201716090515 A US201716090515 A US 201716090515A US 2019112530 A1 US2019112530 A1 US 2019112530A1
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Prior art keywords
biomass
water
immersion
less
solid fuel
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US16/090,515
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Inventor
Shigeya HAYASHI
Tatsumi Tano
Naohide FUJIMOTO
Daisuke MAKI
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Ube Corp
Mitsubishi Ube Cement Corp
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Ube Industries Ltd
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Publication of US20190112530A1 publication Critical patent/US20190112530A1/en
Assigned to UBE CORPORATION reassignment UBE CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: UBE INDUSTRIES, LTD.
Assigned to MITSUBISHI UBE CEMENT CORPORATION reassignment MITSUBISHI UBE CEMENT CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: UBE CORPORATION
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B39/00—Cooling or quenching coke
    • C10B39/04—Wet quenching
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B39/00—Cooling or quenching coke
    • C10B39/16—Cooling or quenching coke combined with sorting
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B45/00—Other details
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/08—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form in the form of briquettes, lumps and the like
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/40—Solid fuels essentially based on materials of non-mineral origin
    • C10L5/44—Solid fuels essentially based on materials of non-mineral origin on vegetable substances
    • C10L5/442—Wood or forestry waste
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L9/00—Treating solid fuels to improve their combustion
    • C10L9/08—Treating solid fuels to improve their combustion by heat treatments, e.g. calcining
    • C10L9/086—Hydrothermal carbonization
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D7/00—Devices using evaporation effects without recovery of the vapour
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/02—Combustion or pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/06—Heat exchange, direct or indirect
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/18—Spraying or sprinkling
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/32—Molding or moulds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
    • C10L5/34—Other details of the shaped fuels, e.g. briquettes
    • C10L5/36—Shape
    • C10L5/361—Briquettes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

Definitions

  • the present invention relates to a cooling apparatus for carbonized biomass.
  • Patent Document 1 bio coke having an excellent strength is obtained by pressure-molding pulverized biomass while heating it to effect semi-carbonization.
  • Patent Document 1 Patent No. 4088933
  • the present invention has been made to solve the above problems and an objective of the present invention is to improve the cooling efficiency of semi-carbonized molded biomass while reducing clogging in a facility.
  • the present invention comprises a carbonizing furnace for obtaining carbonized biomass by carbonizing molded biomass; classification means, disposed at downstream side of the carbonizing furnace, for classifying the carbonized biomass; and cooling means, disposed at downstream side of the classification means, for cooling the classified carbonized biomass; wherein the molded biomass is obtained by molding pulverized raw biomass, and the cooling means cools the carbonized biomass by spraying water thereon.
  • FIG. 1 is a graph showing COD and pH versus solid temperature of the biomass solid fuels.
  • FIG. 2 is a graph showing the correlation of the solid temperature of the heating step to grindability index and pulverizing rate of the obtained biomass solid fuels.
  • FIG. 3 is a graph showing a particle size distribution of the biomass solid fuels subjected to disintegration test.
  • FIG. 4 is a graph showing the results of a water immersion test (moisture content of the solid) of biomass solid fuels.
  • FIG. 5 is a graph showing the solid strength (rotation strength) before and after a water immersion test.
  • FIG. 6 is a graph showing the solid strength (mechanical durability) before and after a water immersion test.
  • FIG. 7 is a graph showing BET specific surface area of the solid fuels.
  • FIG. 8 is a graph showing an average pore diameter of the surface of the solid fuels.
  • FIG. 9 is a graph showing a total pore volume of the surface of the solid fuels.
  • FIG. 10 is a graph showing a yield of the biomass solid fuels.
  • FIG. 11 is a graph showing a spontaneous combustion index (SCI) of the biomass solid fuels.
  • FIG. 12 is a cross-sectional photograph before immersion in water of Example A-2.
  • FIG. 13 is a cross-sectional photograph after immersion in water (2 seconds) of Example A-2.
  • FIG. 14 is a cross-sectional photograph after immersion in water (20 seconds) of Example A-2.
  • FIG. 15 is a cross-sectional photograph before immersion in water of Comparative Example A.
  • FIG. 16 is a cross-sectional photograph after immersion in water (2 seconds) of Comparative Example A.
  • FIG. 17 is a cross-sectional photograph after immersion in water (20 seconds) of Comparative Example A.
  • FIG. 18 is a diagram showing (estimated) mechanism of the development of solid cross-links in PBT.
  • FIG. 19 is a chart showing the results of FT-IR analysis of the outer surface of pellets of the biomass solid fuels.
  • FIG. 20 is a chart showing the results of FT-IR analysis of the cross-sectional center of pellets of the biomass solid fuels.
  • FIG. 21 is a chart showing the results of FT-IR analysis of acetone extract solution of the biomass solid fuels.
  • FIG. 22 is a chart showing the results of FT-IR analysis of the solid of biomass solid fuels after acetone extract.
  • FIG. 23 is a chart showing the results of GC-MS analysis of acetone extract solution of the biomass solid fuels.
  • FIG. 24 is a photograph showing the shape of a pellet after immersion in physiological saline solution in Example B.
  • FIG. 25 is a diagram showing the distribution of sodium before and after immersion in physiological saline in Example B.
  • FIG. 26A is a schematic view showing a cooling facility for carbonized biomass.
  • FIG. 26B is a schematic view showing another example of the cooling facility for carbonized biomass.
  • FIG. 27 is a diagram showing a process flow of the present invention.
  • FIG. 28 is a diagram showing a control flow.
  • FIG. 26A is a schematic view of the present invention and FIG. 27 is a process flow.
  • a biomass solid fuel obtained by a fuel manufacturing step 100 in FIG. 27 becomes a product through a classification step 200 and a cooling step 300 .
  • the biomass solid fuel is manufactured by using known method.
  • Raw biomass is molded in a molding step 120 after a crushing-pulverizing step 110 , then the molded biomass is heated by using a kiln 1 in FIG. 26A in a heating step 130 .
  • No binding agent such as binder is added in the molding step 120 , and the pulverized biomass particles is simply compressed or pressed for molding.
  • the unheated molded biomass just after the molding step 120 (White Pellet: referred to as WP below) has a low strength since it is obtained by just pressing and molding pulverized biomass, therefore it tends to disintegrate easily during handling. Further, it expands and disintegrates by absorbing water.
  • the fuel manufacturing step 100 of the present invention by heating the molded biomass at 150 to 400° C. (low-temperature carbonizing) in heating step 130 (kiln 1 ), a biomass solid fuel (Pelletizing Before Torrefaction: referred to as PBT below) having high-strength and water-resistance is manufactured, while keeping a shape as a molded product.
  • PBT biomass solid fuel
  • the classification step 200 and the cooling step 300 are carried out by using a vibrating conveyer 2 shown in FIG. 26A .
  • the vibrating conveyer 2 is separated into two sections by a separating plate 24 , in which one of the sections is a classification section 21 and the other is a cooling section 22 .
  • the PBT discharged from the kiln 1 is transported by vibration of a flat plate 22 b and by being pushed by the PBT which is continuously supplied from the kiln 1 .
  • the PBT is discharged as a product through the classification section 21 and the cooling section 22 .
  • the vibrating conveyer 2 in FIG. 26A is inclined, horizontal one that is not inclined can be used.
  • Classification of PBT and fine powder is carried out by vibrating PBT on a sieve 21 a in the classification section 21 . Opening size of the sieve 21 a may be changed accordingly to the desired value. The PBT disintegrated during manufacturing or the PBT smaller than the predetermined size fall down from the sieve 21 a and are treated in other process. The PBT remaining on the sieve is transported to the cooling section 22 .
  • the cooling section 22 has a spraying section 22 a and a vibration flat plate 22 b , wherein the spraying section 22 a is configured to spray water on the flat plate 22 b .
  • the PBT on the flat plate 22 b is cooled by water spraying (cooling step 300 ), and then discharged as a product. It is noted that cooling may be implemented by spraying water only, or by using air cooling together by providing air nozzle or the like in addition to the spraying section 22 a . Moreover, a two-fluid spray nozzle for air and water may be used.
  • the flat plate 22 b is a smooth plate that has no hole and no concave-convex, and a metal plate or a resin plate is used for it. Employment of a smooth plate allows the PBT to slide easily in the cooling section 22 , resulting in smooth transportation in the cooling section 22 .
  • the classification section 21 and the cooling section 22 is separated by the separating plate 24 , it is possible to prevent splayed water within the cooling section 22 from entering into the classification section 21 . Accordingly, water absorption by fine powder which has been classified in the classification section 21 is prevented and thus, clogging in the classification section 21 can be reduced.
  • thermometer 11 is disposed at an outlet of the kiln 1 and a control section 30 is configured to perform spraying water and stopping water spraying based on the measured temperature. It is noted that the thermometer 11 may be disposed at other position as long as it is disposed at such a position that allows the thermometer to measure a temperature of the kiln 1 .
  • PBT having high strength and water-resistance can be obtained by heating WP in the kiln 1 , if the temperature of kiln 1 is at a predetermined value or lower, unheated WP or molded biomass that does not have enough strength and water-resistance will be discharged from the kiln 1 . If they are fed to a vibrating conveyer 2 , since they have poor water-resistance, they will expand and disintegrate after water absorption in the spraying section 22 , and cause clogging in the facility.
  • thermometer 11 if a temperature measured by the thermometer 11 is below a predetermined value, it is judged as a low temperature insufficient for PBT manufacturing and the control section 30 stops spraying water by spraying section 22 a .
  • the control section 30 stops spraying water by spraying section 22 a .
  • FIG. 28 is a flowchart of continuing and stopping of spraying water based on temperature, which is carried out by the control section 30 .
  • a temperature of the outlet of kiln 1 is measured by the thermometer 11 .
  • a step S 2 it is judged whether the measured temperature T is a predetermined value a or lower; if YES then spraying water is stopped in a step S 3 whereas if NO then spraying water is carried out in a step S 4 .
  • thermometer 11 directly measures not an atmosphere temperature of outlet of the kiln 1 but a temperature of PBT at the outlet of the kiln 1 .
  • the PBT solid fuel
  • the excessive temperature increase accelerates carbonization more than necessary and reduces a thermal yield, leading to insufficient fuel properties.
  • accurate temperature control is required; and therefore the temperature of PBT is measured directly to accomplish a high accuracy carbonization.
  • Thermometer 11 may be any type as long as it can directly measure a temperature of PBT at outlet of kiln 1 , and a contact type thermometer or a non-contact type thermometer such as infrared radiation may be used.
  • An apparatus comprises a kiln 1 (a carbonizing furnace) for obtaining carbonized biomass (PBT) by carbonizing molded biomass, a classification section 21 (classification means), disposed at downstream side of the kiln 1 , for classifying the carbonized biomass (PBT), and a cooling section 22 (cooling means), disposed at downstream side of the classification section 21 , for cooling the classified carbonized biomass (PBT), wherein the molded biomass is obtained by molding pulverized raw biomass and wherein the cooling section 22 cools the carbonized biomass (PBT) by spraying water.
  • a kiln 1 a carbonizing furnace
  • classification section 21 classification means
  • cooling section 22 cooling means
  • the cooling section 22 comprises a vibration flat plate 22 b (flat plate) and a splaying section 22 a for spraying water on the flat plate 22 b , wherein the flat plate 22 b is a metal plate or a resin plate, and the carbonized biomass (PBT) is transported by vibration.
  • the flat plate 22 b is a metal plate or a resin plate, and the carbonized biomass (PBT) is transported by vibration.
  • Control section 30 (control means) is provided for stopping spraying water by the spraying section 22 a if a temperature at the outlet of kiln 1 is at a predetermined value or lower.
  • a temperature at the outlet of kiln 1 is at a predetermined value or lower.
  • the temperature of kiln 1 is equal to a predetermined value or lower (low temperature insufficient for manufacturing PBT)
  • non-carbonized molded biomass or insufficiently-carbonized molded biomass with low-strength or low water-resistance is discharged. They may swell and disintegrate, leading to clogging in the facility. However, clogging can be avoided by stopping spraying water.
  • Thermometer 11 can directly measure the temperature of carbonized biomass (PBT). Although water-resistant and high-strength PBT (solid fuel) can be obtained by carbonizing WP at a predetermined temperature or higher, excessive carbonization deteriorates thermal yield. Therefore, by directly measuring the temperature of PBT, highly accurate carbonization can be carried out, allowing the production of the product having water-resistance and high-strength while ensuring thermal yield.
  • PBT carbonized biomass
  • Separating section 24 for separating the classification section 21 and the cooling section 22 is provided. By separating these sections, it is possible to prevent the sprayed water from entering into the classification section 22 , and thus, piling up of the product and clogging during classification are suppressed.
  • a classification step and a cooling step may be carried out using a system as shown in FIG. 26B .
  • the system 402 includes a vibrating sieve apparatus 403 A and a cooling vibrating conveyor 403 B.
  • the vibrating sieve apparatus 403 A and the cooling vibrating conveyor 403 B are configured to have separate bodies.
  • the vibrating sieve apparatus 403 A is disposed at the upstream side of a transport direction of the PBT, and the cooling vibrating conveyor 403 B is disposed at the downstream side.
  • the description for the functions and structures common to the configuration in FIG. 26A will be omitted to avoid redundant description.
  • the vibrating sieve apparatus 403 A has a classifying section 421 provided with a sieve 421 a .
  • PBT is supplied from the rotary kiln (not shown in FIG. 26B ) onto the sieve 421 a .
  • the PBT is transported while being vibrated on the sieve 421 a , whereby classification (classification step) of PBT and fine powder is carried out.
  • the vibrating sieve apparatus 403 A is inclined, a horizontal one that is not inclined can be used.
  • the opening size of the sieve 421 a may be changed appropriately according to a desired value. Those disintegrated during manufacturing or small PBT that do not reach a predetermined size fall under the sieve 421 a and are processed separately. The PBT remaining on the sieve 421 a is discharged from an outlet 421 b of the vibrating sieve apparatus 403 A.
  • the cooling vibrating conveyor 403 B has a cooling section 422 provided with a water spray section 422 a and a vibration flat plate 422 b and the like, and the PBT from the vibrating sieve apparatus 403 A is supplied onto the flat plate 422 b .
  • the cooling vibrating conveyor 403 B is also provided with a control section for controlling the operation of the water spray section 422 a and the like, as in the configuration of FIG. 26A .
  • the flat plate 422 b is a smooth plate without holes and concave-convex, and a metal plate or a resin plate is used. Employment of a smooth plate allows the PBT to slide easily, enabling smooth transportation.
  • the cooling vibrating apparatus 403 B is inclined, a horizontal one that is not inclined can be used.
  • cooling may be carried out by water spraying only, or it may be carried out by using air cooling in combination with water spraying.
  • Spray nozzle may be a two-fluid nozzle for air and water.
  • the water spraying by water spray section 422 a may be controlled so as to stop water spraying when the temperature measured by the thermometer 11 of the kiln 1 (see FIG. 26A ) is below a predetermined value. It should be noted that the technical matters disclosed in FIG. 26B can be combined with or replaced with the matters disclosed in other embodiments, without departing from the scope of the present invention.
  • a method of manufacturing the biomass solid fuel (PBT) produced in the above-described fuel manufacturing step 100 will be described in detail as follows.
  • the biomass solid fuel is a molded solid product obtained by the steps including a molding step of compressing and molding biomass that has been crushed and pulverized to a state of debris or powder into biomass blocks, and a heating step of heating the biomass blocks.
  • the molded and heated solid product is used as a fuel (corresponding to PBT mentioned below). Since the biomass solid fuel does not require a step of steam explosion and the use of a binder, the cost increase is suppressed.
  • the biomass blocks obtained by molding process and before the heating step are also referred to as “unheated biomass blocks”.
  • the unheated biomass blocks correspond to the WP as mentioned above.
  • Biomass as a raw material may be any wood-based and herbaceous material, and tree species and parts thereof or the like are not particularly limited, but examples include douglas fir, hemlock, cedar, cypress, European red pine, almond old tree, almond shell, acacia xylem part, acacia bark, walnut shell, sago palm, EFB (empty fruit bunch that is a residue of palm oil processing), meranti, rubber tree and the like. These may be used alone or in a mixture of two or more of these.
  • the biomass blocks are formed by using known molding techniques.
  • the biomass blocks are preferably in a form of pellet or briquette, and the size thereof is arbitrary.
  • the heating step the molded biomass blocks are heated.
  • the COD (Chemical Oxygen Demand) of an immersion water used for water immersion is preferably 3,000 ppm or less.
  • COD ratio represented by (COD of biomass solid fuel after the heating step/COD of unheated biomass solid fuel) of the biomass solid fuel is preferably 0.98 or less.
  • the COD (Chemical Oxygen Demand) of an immersion water used for water immersion of a biomass solid fuel means a COD value assayed in accordance with JIS K0102(2010)-17 for a sample of immersion water for COD determination prepared in accordance with Japan Environment Agency Announcement No. 13 “(A) a method for detecting a metal or the like contained in an industrial waste”, 1973.
  • the biomass solid fuel obtained after the heating step has a Hardgrove grindability index (HOT) in accordance with JIS M 8801 of preferably 15 or more and 60 or less, and more preferably 20 or more and 60 or less. Further, BET specific surface area thereof is 0.15 to 0.8 m 2 /g, and more preferably 0.15 to 0.7 m 2 /g. It is preferable that the equilibrium moisture content after immersion in water is 15 to 65 wt %, and more preferably 15 to 60 wt %.
  • HET Hardgrove grindability index
  • the biomass solid fuel of the present invention has a fuel ratio (fixed carbon/volatile matter) of 0.2 to 0.8, a dry-basis higher heating value of 4,800 to 7000 (kcal/kg), a molar ratio of oxygen O to carbon C (O/C) of 0.1 to 0.7, and a molar ratio of hydrogen H to carbon C (H/C) of 0.8 to 1.3. If the biomass solid fuel has the physical properties within the above ranges, COD of a discharged water during storage can be reduced, disintegration can be reduced and handleability during storage can be improved.
  • the biomass solid fuel of the present invention can be obtained by adjusting, for example, tree species of the biomass used as a raw material, parts of these, and heating temperature in the heating step and the like. Proximate analysis (industrial analysis) value, ultimate analysis (elemental analysis) value, and higher heating value in the present specification are based on JIS M 8812, 8813, and 8814.
  • the method of manufacturing a biomass solid fuel of the present invention comprises a molding step of molding pulverized biomass of the biomass that has been crushed and pulverized to obtain unheated biomass blocks, and a heating step of heating the unheated biomass blocks whereby providing a heated solid product, wherein the heating temperature in the heating step is preferably 150° C. to 400° C. With the temperature of the heating step within the above range, the biomass solid fuel having the above properties can be obtained.
  • the heating temperature is appropriately determined depending on biomass raw materials and the shape and size of biomass blocks, but it is preferably 150 to 400° C., more preferably 200 to 350° C. Further preferably, it is 230 to 300° C. It is yet furthermore preferably 250 to 290° C.
  • the heating time in the heating step is not particularly limited, but it is preferably 0.2 to 3 hours.
  • the particle size of the pulverized biomass is not particularly limited, but the average size is about 100 to 3000 ⁇ m, and preferably 400 to 1000 ⁇ m.
  • known measurement methods may be used. Since mutual bonding or adhesion in the pulverized biomass is maintained by solid cross-linking in the biomass solid fuel (PBT) of the present invention as described below, the particle size of the pulverized biomass is not particularly limited as long as it is within a moldable range. Further, since the fine pulverization becomes a cause of cost increase, the particle size may be within a known range as long as both of cost and moldability can stand together.
  • A denotes the bulk density of the unheated biomass blocks before heating step and B denotes the bulk density of the heated solid product after the heating step
  • B/A 0.7 to 1.
  • the value of the bulk density A is not particularly limited as long as it is within such a known range that unheated biomass blocks can be obtained by molding the pulverized biomass.
  • the bulk density varies depending on the kind of biomass raw materials, and thus it may be appropriately set.
  • H1 denotes HGI (Hardgrove grindability index of JIS M8801) of unheated biomass blocks and H2 denotes HGI of heated solid products
  • characteristics of the biomass solid fuel may be determined in a preferable range depending on tree species of biomass used as a raw material.
  • tree species of biomass used as a raw material For example thereof will be described, but the present invention is not limited to these tree species and combinations thereof.
  • preferred ranges will be described about species of biomass raw materials used in the present invention and properties of the obtained solid fuels (corresponding to PBT as mentioned below) and their manufacturing method, respectively.
  • a biomass solid fuel (hereinafter, may be referred to as a solid fuel A) is as follows.
  • COD thereof is preferably 1000 ppm or less, more preferably 900 ppm or less, further more preferably 800 ppm or less, and COD ratio thereof is preferably 0.80 or less, more preferably 0.70 or less, and further more preferably 0.68 or less.
  • the equilibrium moisture content after immersion in water thereof is preferably 15 wt % to 45 wt %, more preferably 18 wt % to 35 wt %, and further more preferably 18 wt % to 32 wt %.
  • the BET specific surface area thereof is preferably 0.25 m 2 /g to 0.8 m 2 /g, more preferably 0.28 m 2 /g to 0.6 m 2 /g, and further more preferably 0.32 m 2 /g to 0.5 m 2 /g.
  • the HGI thereof is preferably 20 to 60, more preferably 20 to 55, and further more preferably 22 to 55. Since HGI of coal (bituminous coal) suitable as a boiler fuel for electric power generation is about 50, HGI closer to about 50 is preferable, considering that it is mixed and ground with coal. HGI ratio (described later) is preferably 1.0 to 2.5.
  • the fuel ratio thereof is preferably 0.2 to 0.8, more preferably 0.2 to 0.7, and further more preferably 0.2 to 0.65.
  • the dry-basis higher heating value thereof is preferably 4800 to 7000 kcal/kg, more preferably from 4900 to 7000 kcal/kg, and further more preferably 4950 to 7000 kcal/kg.
  • the molar ratio of oxygen O to carbon C (O/C) thereof is preferably 0.1 to 0.62, more preferably 0.1 to 0.61, and further more preferably 0.1 to 0.60.
  • the molar ratio of hydrogen H to carbon C (H/C) thereof is preferably 0.8 to 1.3, more preferably 0.85 to 1.3, and further more preferably 0.9 to 1.3.
  • the heating temperature in the heating step is preferably 200 to 350° C., more preferably 210 to 330° C., and further more preferably 220 to 300° C.
  • a biomass solid fuel (hereinafter, may be referred to as a solid fuel B) is as follows.
  • COD thereof is preferably 900 ppm or less, more preferably 800 ppm or less, further more preferably 700 ppm or less, and COD ratio thereof is preferably 0.75 or less, more preferably 0.68 or less, and further more preferably 0.64 or less.
  • the equilibrium moisture content after immersion in water thereof is preferably 15 wt % to 45 wt %, more preferably 18 wt % to 40 wt %, and further more preferably 18 wt % to 31 wt %.
  • the BET specific surface area thereof is preferably 0.30 m 2 /g to 0.7 m 2 /g, more preferably 0.30 m 2 /g to 0.6 m 2 /g, and further more preferably 0.30 m 2 /g to 0.5 m 2 /g.
  • the HGI thereof is preferably 25 to 60, more preferably 30 to 55, and further more preferably 35 to 55.
  • HGI ratio (described later) is preferably 1.0 to 2.5.
  • the fuel ratio thereof is preferably 0.2 to 0.8, more preferably 0.2 to 0.7, and further more preferably 0.2 to 0.65.
  • the dry-basis higher heating value thereof is preferably 4950 to 7000 kcal/kg, more preferably from 5000 to 7000 kcal/kg, and further more preferably 5100 to 7000 kcal/kg.
  • the molar ratio of oxygen O to carbon C (O/C) thereof is preferably 0.1 to 0.60, more preferably 0.2 to 0.60, and further more preferably 0.3 to 0.60.
  • the molar ratio of hydrogen H to carbon C (H/C) thereof is preferably 0.8 to 1.3, more preferably 0.85 to 1.3, and further more preferably 0.9 to 1.3.
  • the heating temperature in the heating step is preferably 200 to 350° C., more preferably 220 to 300° C., and further more preferably 240 to 290° C.
  • a biomass solid fuel (hereinafter, may be referred to as a solid fuel C) is as follows.
  • COD thereof is preferably 2100 ppm or less, more preferably 2000 ppm or less, further more preferably 1500 ppm or less, and COD ratio thereof is preferably 0.80 or less, more preferably 0.75 or less, and further more preferably 0.55 or less.
  • the equilibrium moisture content after immersion in water thereof is preferably 25 wt % to 60 wt %, more preferably 30 wt % to 50 wt %, and further more preferably 30 wt % to 45 wt %.
  • the BET specific surface area thereof is preferably 0.20 m 2 /g to 0.70 m 2 /g, more preferably 0.22 m 2 /g to 0.65 m 2 /g, and further more preferably 0.25 m 2 /g to 0.60 m 2 /g.
  • the HGI thereof is preferably 15 to 60, more preferably 18 to 55, and further more preferably 20 to 55.
  • HGI ratio (described later) is preferably 1.0 to 2.0.
  • the fuel ratio thereof is preferably 0.2 to 0.8, more preferably 0.25 to 0.7, and further more preferably 0.3 to 0.65.
  • the dry-basis higher heating value thereof is preferably 4800 to 7000 kcal/kg, more preferably from 4800 to 6500 kcal/kg, and further more preferably 4900 to 6500 kcal/kg.
  • the molar ratio of oxygen O to carbon C (O/C) thereof is preferably 0.10 to 0.70, more preferably 0.20 to 0.60, and further more preferably 0.30 to 0.60.
  • the molar ratio of hydrogen H to carbon C (H/C) thereof is preferably 0.8 to 1.3, more preferably 0.85 to 1.3, and further more preferably 0.9 to 1.20.
  • the heating temperature in the heating step is preferably 200 to 350° C., more preferably 220 to 300° C., and further more preferably 240 to 290° C.
  • a biomass solid fuel (hereinafter, may be referred to as a solid fuel D) is as follows.
  • COD thereof is preferably 2500 ppm or less, more preferably 2000 ppm or less, further more preferably 1500 ppm or less, and COD ratio thereof is preferably 0.75 or less, more preferably 0.68 or less, and further more preferably 0.50 or less.
  • the equilibrium moisture content after immersion in water thereof is preferably 15 wt % to 50 wt %, more preferably 20 wt % to 40 wt %, and further more preferably 20 wt % to 35 wt %.
  • the BET specific surface area thereof is preferably 0.20 m 2 /g to 0.70 m 2 /g, more preferably 0.27 m 2 /g to 0.70 m 2 /g, and further more preferably 0.30 m 2 /g to 0.60 m 2 /g.
  • the HGI thereof is preferably 20 to 60, more preferably 20 to 55, and further more preferably 23 to 55.
  • HGI ratio (described later) is preferably 1.0 to 2.0.
  • the fuel ratio thereof is preferably 0.2 to 0.8, more preferably 0.30 to 0.7, and further more preferably 0.35 to 0.65.
  • the dry-basis higher heating value thereof is preferably 4800 to 7000 kcal/kg, more preferably from 4800 to 6500 kcal/kg, and further more preferably 4900 to 6300 kcal/kg.
  • the molar ratio of oxygen O to carbon C (O/C) thereof is preferably 0.10 to 0.70, more preferably 0.20 to 0.60, and further more preferably 0.30 to 0.55.
  • the molar ratio of hydrogen H to carbon C (H/C) thereof is preferably 0.8 to 1.3, more preferably 0.8 to 1.25, and further more preferably 0.85 to 1.20.
  • the heating temperature in the heating step is preferably 200 to 350° C., more preferably 220 to 300° C., and further more preferably 240 to 290° C.
  • a biomass solid fuel (hereinafter, may be referred to as a solid fuel E) is as follows.
  • COD thereof is preferably 950 ppm or less, more preferably 850 ppm or less, further more preferably 800 ppm or less, and COD ratio thereof is preferably 0.95 or less, more preferably 0.85 or less, and further more preferably 0.80 or less.
  • the equilibrium moisture content after immersion in water thereof is preferably 20 wt % to 60 wt %, more preferably 20 wt % to 55 wt %, and further more preferably 23 wt % to 53 wt %.
  • the BET specific surface area thereof is preferably 0.40 m 2 /g to 0.70 m 2 /g, more preferably 0.50 m 2 /g to 0.70 m 2 /g, and further more preferably 0.55 m 2 /g to 0.70 m 2 /g.
  • the fuel ratio thereof is preferably 0.2 to 0.6, more preferably 0.2 to 0.5, and further more preferably 0.2 to 0.4.
  • the dry-basis higher heating value thereof is preferably 4800 to 7000 kcal/kg, more preferably from 4800 to 6000 kcal/kg, and further more preferably 4800 to 5500 kcal/kg.
  • the molar ratio of oxygen O to carbon C (O/C) thereof is preferably 0.40 to 0.70, more preferably 0.45 to 0.70, and further more preferably 0.48 to 0.65.
  • the molar ratio of hydrogen H to carbon C (H/C) thereof is preferably 0.8 to 1.3, more preferably 1.0 to 1.3, and further more preferably 1.1 to 1.3.
  • the heating temperature in the heating step is preferably 200 to 350° C., more preferably 220 to 300° C., and further more preferably 240 to 290° C.
  • a biomass solid fuel (hereinafter, may be referred to as a solid fuel F) is as follows.
  • COD thereof is preferably 2500 ppm or less, more preferably 2000 ppm or less, further more preferably 1200 ppm or less, and COD ratio thereof is preferably 0.30 or less, more preferably 0.20 or less, and further more preferably 0.15 or less.
  • the equilibrium moisture content after immersion in water thereof is preferably 15 wt % to 50 wt %, more preferably 20 wt % to 45 wt %, and further more preferably 25 wt % to 40 wt %.
  • the BET specific surface area thereof is preferably 0.35 m 2 /g to 0.55 m 2 /g, more preferably 0.40 m 2 /g to 0.55 m 2 /g, and further more preferably 0.40 m 2 /g to 0.50 m 2 /g.
  • the fuel ratio thereof is preferably 0.4 to 0.8, more preferably 0.42 to 0.75, and further more preferably 0.45 to 0.75.
  • the dry-basis higher heating value thereof is preferably 4800 to 7000 kcal/kg, more preferably from 5000 to 7000 kcal/kg, and further more preferably 5200 to 6500 kcal/kg.
  • the molar ratio of oxygen O to carbon C (O/C) thereof is preferably 0.25 to 0.60, more preferably 0.30 to 0.60, and further more preferably 0.30 to 0.55.
  • the molar ratio of hydrogen H to carbon C (H/C) thereof is preferably 0.8 to 1.3, more preferably 0.8 to 1.2, and further more preferably 0.9 to 1.2.
  • the heating temperature in the heating step is preferably 200 to 350° C., more preferably 220 to 300° C., and further more preferably 240 to 290° C.
  • a biomass solid fuel (hereinafter, may be referred to as a solid fuel G) is as follows.
  • COD thereof is preferably 2500 ppm or less, more preferably 2100 ppm or less, further more preferably 1500 ppm or less, and COD ratio thereof is preferably 0.65 or less, more preferably 0.55 or less, and further more preferably 0.45 or less.
  • the equilibrium moisture content after immersion in water thereof is preferably 20 wt % to 45 wt %, more preferably 20 wt % to 40 wt %, and further more preferably 25 wt % to 35 wt %.
  • the BET specific surface area thereof is preferably 0.15 m 2 /g to 0.35 m 2 /g, more preferably 0.19 m 2 /g to 0.33 m 2 /g, and further more preferably 0.20 m 2 /g to 0.30 m 2 /g.
  • the HGI thereof is preferably 18 to 60, and more preferably 20 to 60.
  • HGI ratio (described later) is preferably 1.0 or more.
  • the fuel ratio thereof is preferably 0.2 to 0.7, more preferably 0.25 to 0.65, and further more preferably 0.28 to 0.60.
  • the dry-basis higher heating value thereof is preferably 4800 to 7000 kcal/kg, more preferably from 4800 to 6000 kcal/kg, and further more preferably 5000 to 6000 kcal/kg.
  • the molar ratio of oxygen O to carbon C (O/C) thereof is preferably 0.30 to 0.65, more preferably 0.40 to 0.70, and further more preferably 0.40 to 0.60.
  • the molar ratio of hydrogen H to carbon C (H/C) thereof is preferably 0.8 to 1.3, more preferably 0.9 to 1.25, and further more preferably 0.9 to 1.2.
  • the heating temperature in the heating step is preferably 200 to 350° C., more preferably 220 to 300° C., and further more preferably 240 to 290° C.
  • a biomass solid fuel (hereinafter, may be referred to as a solid fuel H) is as follows.
  • COD thereof is preferably 2000 ppm or less, more preferably 1600 ppm or less, further more preferably 800 ppm or less, and COD ratio thereof is preferably 0.85 or less, more preferably 0.60 or less, and further more preferably 0.4 or less.
  • the equilibrium moisture content after immersion in water thereof is preferably 20 wt % to 35 wt %, more preferably 20 wt % to 33 wt %, and further more preferably 22 wt % to 30 wt %.
  • the BET specific surface area thereof is preferably 0.15 m 2 /g to 0.35 m 2 /g, more preferably 0.18 m 2 /g to 0.33 m 2 /g, and further more preferably 0.18 m 2 /g to 0.30 m 2 /g.
  • the HGI thereof is preferably 20 to 60, more preferably 25 to 55, and further more preferably 30 to 55.
  • HGI ratio (described later) is preferably 1.0 to 2.5, more preferably 1.3 to 2.3 and further more preferably 1.5 to 2.2.
  • the fuel ratio thereof is preferably 0.2 to 0.8, more preferably 0.25 to 0.8, and further more preferably 0.5 to 0.8.
  • the dry-basis higher heating value thereof is preferably 4800 to 7000 kcal/kg, more preferably from 4900 to 6500 kcal/kg, and further more preferably 5000 to 6000 kcal/kg.
  • the molar ratio of oxygen O to carbon C (O/C) thereof is preferably 0.20 to 0.65, more preferably 0.20 to 0.60, and further more preferably 0.2 to 0.55.
  • the molar ratio of hydrogen H to carbon C (H/C) thereof is preferably 0.8 to 1.3, more preferably 0.85 to 1.3, and further more preferably 0.85 to 1.2.
  • the heating temperature in the heating step is preferably 200 to 350° C., more preferably 220 to 300° C., and further more preferably 240 to 290° C.
  • a raw material is EFB (empty fruit bunch that is residue of palm oil processing)
  • the properties of a biomass solid fuel is as follows.
  • COD thereof is preferably 2350 ppm or less, more preferably 2300 ppm or less, further more preferably 2000 ppm or less, and COD ratio thereof is preferably 0.98 or less, more preferably 0.96 or less, and further more preferably 0.85 or less.
  • the equilibrium moisture content after immersion in water thereof is preferably 23 wt % to 45 wt %, more preferably 20 wt % to 40 wt %, and further more preferably 20 wt % to 35 wt %.
  • the BET specific surface area thereof is preferably 0.25 m 2 /g to 0.65 m 2 /g, more preferably 0.30 m 2 /g to 0.60 m 2 /g, and further more preferably 0.35 m 2 /g to 0.55 m 2 /g.
  • the fuel ratio thereof is preferably 0.25 to 0.8, more preferably 0.30 to 0.8, and further more preferably 0.36 to 0.8.
  • the dry-basis higher heating value thereof is preferably 4800 to 7000 kcal/kg, more preferably from 4900 to 7000 kcal/kg, and further more preferably 5000 to 7000 kcal/kg.
  • the molar ratio of oxygen O to carbon C (O/C) thereof is preferably 0.15 to 0.65, more preferably 0.15 to 0.60, and further more preferably 0.15 to 0.55.
  • the molar ratio of hydrogen H to carbon C (H/C) thereof is preferably 0.5 to 1.3, more preferably 0.55 to 1.3, and further more preferably 0.6 to 1.2.
  • the heating temperature in the heating step is preferably 200 to 350° C., more preferably 220 to 300° C., and further more preferably 240 to 260° C.
  • a biomass solid fuel (hereinafter, may be referred to as a solid fuel J) is as follows.
  • COD thereof is preferably 330 ppm or less, more preferably 320 ppm or less, further more preferably 300 ppm or less, and COD ratio thereof is preferably 0.98 or less, more preferably 0.95 or less, and further more preferably 0.90 or less.
  • the equilibrium moisture content after immersion in water thereof is preferably 15 wt % to 30 wt %, more preferably 15 wt % to 27 wt %, and further more preferably 18 wt % to 25 wt %.
  • the fuel ratio thereof is preferably 0.2 to 0.6, more preferably 0.2 to 0.5, and further more preferably 0.2 to 0.45.
  • the dry-basis higher heating value thereof is preferably 4800 to 7000 kcal/kg, more preferably from 4800 to 6500 kcal/kg, and further more preferably 4800 to 6000 kcal/kg.
  • the molar ratio of oxygen O to carbon C (O/C) thereof is preferably 0.3 to 0.60, more preferably 0.35 to 0.60, and further more preferably 0.40 to 0.60.
  • the molar ratio of hydrogen H to carbon C (H/C) thereof is preferably 0.9 to 1.2, more preferably 0.95 to 1.2, and further more preferably 1.0 to 1.2.
  • the heating temperature in the heating step is preferably 200 to 350° C., more preferably 220 to 300° C., and further more preferably 230 to 290° C.
  • a biomass solid fuel (hereinafter, may be referred to as a solid fuel K) is as follows.
  • the fuel ratio thereof is preferably 0.2 to 0.8, and more preferably 0.2 to 0.7.
  • the dry-basis higher heating value is preferably 4800 to 7000 kcal/kg.
  • the molar ratio of oxygen O to carbon C (O/C) thereof is preferably 0.1 to 0.70.
  • the molar ratio of hydrogen H to carbon C (H/C) thereof is preferably 0.8 to 1.3.
  • the heating temperature in the heating step is preferably 200 to 350° C., more preferably 220 to 300° C., and further more preferably 230 to 290° C.
  • the present inventors presume that, in the method of manufacturing the biomass solid fuel, because the method has such an order of the steps that the heating step of heating the unheated biomass blocks is performed after the molding step, mutual bonding or adhesion in the pulverized biomass is maintained by using components originated from the raw material biomass without using a binder, which enables the production of biomass solid fuels having high water-resistant which do not disintegrate by immersion in water. According to the analysis of the present inventors, the following findings are obtained regarding the mechanism that the biomass solid fuels acquire water resistance.
  • the present inventors performed FT-IR analysis, GC-MS analysis, and SEM observation about three types of biomass solid fuels manufactured by different production methods, specifically an unheated solid fuel obtained by molding pulverized biomass (White Pellet: hereinafter may be referred to as WP), and a solid fuel obtained by heating after molding pulverized biomass (Pelletizing Before Torrefaction; hereinafter may be referred to as PBT), and analyzed the mechanism of water resistance of the biomass solid fuels.
  • WP unheated solid fuel obtained by molding pulverized biomass
  • PBT Solid fuel obtained by heating after molding pulverized biomass
  • binders were not used either in WP and PBT.
  • acetone extracts of the respective solid fuels were analyzed by FT-IR.
  • content of hydrophilic COOH groups is in small, but content of C ⁇ C bond is large as compared with the unheated WP. This suggests that the chemical structure of the components constituting the biomass has changed and has become hydrophobic by heating.
  • abietic acid and the like terpenes such as abietic acid and derivatives thereof (hereinafter, may be referred to as “abietic acid and the like”) have thermally decomposed by heating, and this fact relates to the water resistance of the biomass solid fuel.
  • the abietic acid and the like are main components of rosins contained in pine and the like.
  • FIG. 18 is a diagram illustrating a (estimated) mechanism of the development of solid cross-linking in PBT.
  • melted liquid of the abietic acid elutes in the gap between biomass (the gap between adjacent pulverized biomass particles that have been compacted by molding after pulverizing; herein the biomass may be referred to as pulverized biomass) with the rise of temperature, and the evaporation and thermal decomposition of abietic acid take place to form hydrophobic materials, which are fixed in the gap between the pulverized biomass particles to develop cross-linkage (solid cross-linkage).
  • the melting point of abietic acid or derivatives thereof is about 139 to 142° C., and the boiling point is about 250° C.
  • abietic acid and the like melt by heating at temperature near the melting point to form liquid cross-linkage, and abietic acid and the like decompose thermally at temperature near the boiling point to develop the formation of solid cross-linkage.
  • terpenes including abietic acid
  • biomass in general (see, Hokkaido Forest Products Research Institute monthly report 171, April 1966, Public Interest Incorporated Association Japan Wood Protection Association, “Wood Preservation” Vol. 34-2 (2008), etc.).
  • all of ⁇ Example A> to ⁇ Example I> described below showed the generation of water resistance by heating 230° C. or higher (disintegration does not occur even after immersion in water, see Table 6), and therefore it is considered that the heating the biomass in general at temperature at least 230° C. or higher to 250° C. or higher provides water resistance.
  • FIGS. 19 to 22 are charts showing the results of FT-IR analysis of a biomass solid fuel of the present invention.
  • the raw material is a European pine of Example B below, and the analysis was made to a heated solid fuel (PBT) obtained by pulverizing and molding the raw material to a pellet form and heating at 250° C.
  • PBT heated solid fuel
  • WP unheated solid fuel
  • FIG. 19 Both in the outer surface of the pellet ( FIG. 19 ) and in cross-sectional center ( FIG. 20 ), the amount of COOH groups is WP>PBT, and the amount of C ⁇ C bonds is PBT>WP. Further, the amount of COOH group eluted into acetone extract ( FIG.
  • FIG. 23 is a chart showing the results of GC-MS analysis of the acetone extract solution.
  • the raw materials is a European pine of Example B as is the same for the above-mentioned FIGS. 19 to 22 , and the analysis was made to a heated solid fuel (PBT) obtained by pulverizing and molding the raw material to a pellet form and heating at 250° C. and an unheated solid fuel (WP).
  • PBT heated solid fuel
  • WP unheated solid fuel
  • the eluted amount of the abietic acid and the like, which is a kind of terpenes, to acetone is smaller in the case of PBT than in the case of WP.
  • the results are considered showing that abietic acid melted by heating to form liquid cross-linkage, and solid cross-linkage was formed by the volatilization of abietic acid and the like.
  • the strength of the solid fuel is improved due to the development of the solid cross-linking, and therefore it is presumed that good grindability (HOT described later, pulverizing rate) and good handleability (disintegration test described below) is obtained without the addition of a binder, by heating at least 230° C. or higher to 250° C. or higher as similar to the water resistance.
  • COD is reduced when PBT is used. This is considered because the tar component of the biomass raw material volatilizes by heating, and at the same time the solidified abietic acid and the like covers the surface of solid fuel PBT, which further increases hydrophobicity of the surface of the solid fuel to prevent the elution of tar component remaining in the biomass raw material.
  • a biomass solid fuel A was obtained through a molding step of pulverizing biomass after crushing and molding the pulverized biomass, and subsequent heating step.
  • the binder is not used in any step.
  • the biomass raw material used is a mixture of douglas fir 40% by weight, hemlock 58% by weight, cedar 1% by weight and cypress 1% by weight.
  • the raw material was molded into a pellet shape with a diameter of 8 mm.
  • 4 kg of raw material is charged in an electric batch furnace having 600 mm diameter and heated to target temperatures (heating temperature in Table 1) in respective Examples with a heating rate of 2° C./min.
  • target temperature and the heating temperature refer to the same meaning.
  • Example A-1 to A-6 temperature was not maintained at the target temperature (heating temperature) (this also applies to the following Examples B to K).
  • Table 1 shows the heating temperature of the heating step in Examples A-1 to A-6 and the properties of the resulting biomass solid fuel A obtained after the heating step.
  • Comparative Example A is an unheated biomass solid fuel (WP) which is obtained only by molding after crushing and pulverizing, and is not through the heating step. A binder is not used also in Comparative Example A. Raw biomass is the same as in Example A-1. Table 1 also shows the properties of the resulting solid fuel of Comparative Example A.
  • WP unheated biomass solid fuel
  • HGI is based on JIS M 8801 as described, and the larger value indicates better grindability.
  • Table 1 shows a higher heating value (dry-basis), a fuel ratio calculated based on proximate analysis values (air dried basis), and results of ultimate analysis values (air dried basis) and molar ratios of oxygen O, carbon C and hydrogen H obtained based on the ultimate analysis.
  • FIG. 1 shows the correlations of the heating temperature in the heating step and COD (chemical oxygen demand) and pH (pH is described below) in the immersion water when the resulting biomass solid fuels were immersed in water.
  • a sample of immersion water for COD determination was prepared in accordance with Japan Environment Agency Announcement No. 13 “(A) a method for detecting a metal or the like contained in an industrial waste”, 1973, and COD was analyzed in accordance with JIS K0102(2010)-17.
  • COD of Comparative Example A (WP: biomass solid fuel obtained by only molding without heating step) is high, i.e. approximately 1200 ppm.
  • COD values of the biomass solid fuels that have been heated at 230° C. or higher are less 800 ppm, indicating that the elution of tar component is low.
  • the biomass solid fuels of Example A-1 to A-6 are fuels having excellent handling properties because the elution of tar component is low even during outdoor storage.
  • the COD values of the biomass solid fuels of Examples A-1 to A-6 heated at 230° C. or higher decrease as the heating temperature becomes higher. This is presumed that the COD value decreases by volatilization of tar or the like due to heating. Therefore, even in the case where the heating temperature is lower than 230° C., namely the heating temperature is 150° C. or higher and lower than 230° C., lower COD values is expected in comparison with the values of Comparative Example A.
  • FIG. 1 shows that although slightly low values are observed for Example A-2 and Example A-3, pH values are approximately about 6 in all of Examples A-1 to A-6, indicating that there is no particular change as compared with unheated Comparative Example A. Therefore, it is shown that no particular problem occurs concerning pH values of the discharged water when Examples A-1 to A-6 are stored outdoor.
  • FIG. 2 shows a relationship between heating temperature in the heating step and Hradgrove grindability Index (HGI) and pulverizing rate (described later) of the obtained biomass solid fuel A, for the biomass solid fuels in Comparative Example A and Examples A-1 to A-6.
  • HGI Hradgrove grindability Index
  • HGI values were altered by heating in Examples A-1 to A-6, and HGI values (based on JIS M 8801) were higher than that of Comparative Examples A (WP: unheated biomass solid fuel after molding).
  • a typical HGI value for coal (bituminous coal) is around 50, and pulverizing properties of Examples A-1 to A-6 are closer to coal and better than Comparative Example A.
  • the pulverizing rate in FIG. 2 is a ground weight per a unit time (g/min) as determined by measuring the weight of a ground sample which is a fraction passing through a 150 ⁇ m sieve after pulverizing a sample of 700 cc with a ball mill.
  • measuring was carried out by using a ball mill conforming to JIS M4002, wherein into a cylindrical container having an inner diameter of 305 mm ⁇ axial length of 305 mm, normal grade ball bearings as defined in JIS B1501 ( ⁇ 36.5 mm ⁇ 43 balls, ⁇ 30.2 mm ⁇ 67 balls, ⁇ 24.4 mm ⁇ 10 balls, ⁇ 19.1 mm ⁇ 71 balls and ⁇ 15.9 mm ⁇ 94 balls) were charged and the container was rotated at a speed of 70 rpm. Heating improves the pulverizing rate, in particular, heating at 230° C. or higher considerably increases the pulverizing rate.
  • Table 2 shows cumulative sieve-passed percentage of the biomass solid fuel A after subjected to the disintegration test
  • FIG. 3 is a particle size distribution diagram.
  • disintegration test was performed. 1 kg of sample was packed into a plastic bag and was dropped 20 times from a height of 8.6 m, and subjected to rotational strength test based on JIS Z 8841, to measure the particle size distribution. The resulting particle size distribution is shown in FIG. 3 .
  • a sample having a particle size distribution in which an amount of 2 mm sieve-passed particles is 30 wt % or less and an amount of 0.5 mm sieve-passed particles is 15 wt % or less is determined as a sample having a handleable particle size in storage and the like.
  • Table 2 and FIG. 3 show that while the sample particle size after rotation strength test has become finer as the heating temperature becomes higher, all samples clear the evaluation criteria described above and therefore they are handleable without any problem.
  • Table 3 and FIG. 4 show the results of a water immersion test of biomass solid fuels A.
  • Solid fuels from respective Examples and Comparative Example were immersed in water and removed after a predetermined time shown in Table 3 and FIG. 4 . After wiping off water, a moisture content of the solid was measured.
  • the solid fuel of Comparative Example A (WP) was disintegrated by immersion in water, and the measurement of moisture content of the solid was impossible.
  • the moisture content reached equilibrium in about 10 hours after immersion, and the equilibrium moisture content was about 27 wt %.
  • the moisture content reached the equilibrium after about 100 hours, and equilibrium moisture content was about 25 wt %.
  • FIG. 5 shows the results of solid strength measured before and after the immersion in water (based on JIS Z-8841 rotational strength test method) for Examples A-1 to A-6 and Comparative Example A.
  • the solid fuel of Comparative Example A (WP) was disintegrated by immersion in water, and the measurement of rotational strength after immersion was impossible.
  • samples used are those dried for 22 hours at 35° C. in a thermostat oven, after wiping off water on the surface of the solid fuels that have reached the equilibrium moisture content.
  • the strength did not substantially decrease, and powdering hardly occurred even compared with Comparative Example A before water immersion (WP), and thus it can be said that the handleability is maintained.
  • FIG. 6 is a diagram showing the result measured for the mechanical durability before and after immersion in water.
  • mechanical durability DU was determined based on the following equation in accordance with the United States agriculture industry's standard ASAE S 269.4 and German Industrial Standard DIN EN 15210-1.
  • m0 is a sample weight before rotation treatment
  • m1 is a sieve-on weight of sample after the rotation treatment, wherein the sieve used was a plate sieve having circle holes with 3.15 mm diameter.
  • Spontaneous combustion property was evaluated based on “Spontaneous combustion test” in “the Manual of Tests and Criteria, the United Nations: Regulations for the Carriage and Storage of Dangerous Goods by Ship, 16th revised edition”.
  • 1 to 2 cm 3 of the biomass solid fuel of Example A-2 (heating temperature: 250° C.) was dropped to an inorganic insulation board from a height of 1 m, and determined whether ignition during falling or within five minutes after falling occurs. The test was made six times. Since the ignition did not occur in 6 trials, Example A-2 (PBT) was determined that it does not fall to the packing grade I of the above UN Manual of Tests and Criteria.
  • FIG. 7 is a diagram showing the results of measurement of BET specific surface area of the solid fuel the A.
  • BET specific surface area was determined using an automatic specific surface area/pore size distribution measuring apparatus (Nippon Bell Co., Ltd. BELSORP-min II) for samples of solid fuels of Examples A-1 to A-6 and Comparative Example A that had been cut into a size of 2 to 6 mm, filled in a container, and degassed in vacuo for 2 hours at 100° C. as a pretreatment. Nitrogen gas was used as an adsorption gas. From FIG. 7 , BET specific surface area increases with the increase of heating temperature, showing that pores developed with heating (pyrolysis).
  • FIG. 8 is a diagram showing the average pore diameter at surface of solid fuel A
  • FIG. 9 is a diagram showing the total pore volume.
  • Average pore diameter and total pore volume were measured using the same equipment used for BET specific surface area.
  • the term “pore” used herein means cavity having a diameter of 2 nm to 100 nm. The average pore diameter becomes smaller with the increase in heating temperature as in Example A-2 and subsequent Examples, indicating that a large number of finer pores were generated. This is believed to be due to decomposition of cellulose.
  • FIG. 10 is a diagram showing a yield of biomass solid fuel A after the heating step (solid yield and thermal yield).
  • Solid yield is a weight ratio before and after heating
  • thermal yield is ratio of heating value before and after heating.
  • the biomass solid fuel A (PBT) can be obtained with low cost, in which COD reduction, improvement in grindability, reduction of water absorption, improvement in solid strength and improvement in yield have been achieved.
  • Spontaneous combustion property of the solid fuel of Example A-2 was measured according to the following method. 1 kg of samples was charged in a container, and placed in a thermostat oven at 80° C. Air was flowed to the sample, and the concentrations of O2, CO, and CO2 in the resulting gas was measured. Amount of O2 adsorption, amount of CO formation, amount of CO2 formation by heating samples are calculated from the concentration before and after heating, based on the following equation (1) to calculate the self-heating index (SCI).
  • SCI self-heating index
  • Spontaneous combustion index (SCI) ⁇ amount of O2 adsorption ⁇ heat of O2 adsorption ⁇ ( 1/100) ⁇ + ⁇ amount of CO formation ⁇ (heat of CO formation+(1 ⁇ 2) ⁇ heat of H2O formation ⁇ H/C) ⁇ ( 1/100) ⁇ + ⁇ amount of CO2 formation ⁇ (heat of CO2 formation+(1 ⁇ 2) ⁇ heat of H2O formation ⁇ H/C) ⁇ ( 1/100) ⁇ formula (1)
  • Amount of adsorption, amount of formation, and H/C of the solid fuel of Example A-2 are as follows.
  • H/C (molar ratio of hydrogen and carbon in the solid fuel of Example A-2) 1.28 [mol/mol] (see Table 1)
  • SCI of Examples A-1 to A-3, A-6 and SCI of Example A-2 after disintegration test was calculated. The calculation results are shown in FIG. 11 .
  • SCI of bituminous coal in Table 4 is also shown in FIG. 11 .
  • the horizontal axis of FIG. 11 is moisture content of arrival-basis, and SCI values of bituminous coal in FIG. 11 are calculated for four samples which are prepared by adding water to the bituminous coal shown in Table 4 to provide four samples with different moisture content.
  • the lower value of the SCI indicates lower spontaneous combustion property as shown by formula (1). Therefore, when Examples A-1 to A-3, A-6, Example A-2 after disintegration test (see, Table 2 and FIG. 3 ), and bituminous coal are compared, if the moisture content is comparable, the biomass solid fuels (PBT) of the present invention have lower SCI (spontaneous combustion index) than bituminous coal and thus have the same level of SCI (spontaneous combustion index) as of bituminous coal having high moisture content. Accordingly, the biomass solid fuel A (PBT) can be said to be good fuel having a reduced risk of ignition during handling.
  • FIGS. 12 to 14 are cross-sectional SEM photographs of the solid fuels of Example A-2 (PBT) before and after immersion in water.
  • FIG. 12 is a photograph before immersion
  • FIG. 13 is a photograph at 2 seconds after immersion
  • FIG. 14 is a photograph at 20 seconds after immersion.
  • FIGS. 15 to 17 are cross-sectional SEM photographs of the solid fuels of Comparative Example A (WP) before and after immersion in water.
  • FIG. 15 is a photograph before immersion
  • FIG. 16 is a photograph at 2 seconds after immersion
  • FIG. 17 is a photograph at 20 seconds after immersion.
  • a cross-section after immersion means a cross section obtained by cutting the solid fuel after 2 seconds or 20 seconds after immersion.
  • the magnification and scale are each shown at bottom part of photographs.
  • Comparative Example A is a molded product of ground biomass, the biomass absorbed water by immersion whereby enlarging pores (gaps between pulverized biomass particles). Thus, it is considered that water further enters the enlarged pores to separate the ground biomasses from each other, causing disintegration of the solid fuel itself (see, FIG. 4 ).
  • Example A-2 In contrast, in the surface of solid fuel of Example A-2 ( FIGS. 12 to 14 ), pores did not expand so much even after immersion in water, and the change by immersion was small. It is presumed that in Example A-2, solid cross-linking developed between pulverized biomass particles by heating, and the water absorption has become difficult due to improved hydrophobicity, causing little change by immersion. Therefore, because the bonding or adhesion between biomass that have been crushed is maintained by solid cross-linking even after immersion, disintegration as in Comparative Example A is less likely to take place. Therefore, in the heated solid fuels of Examples A-1 to A-6 (PBT), as shown in FIG. 4 , biomass solid fuels were obtained in which disintegration was reduced when exposed to rain water and the like, and handling properties during outdoor storage was ensured.
  • PBT heated solid fuels of Examples A-1 to A-6
  • Example B-1 to B-4 PBT
  • the biomass raw material was heated to target temperatures (heating temperatures described in Table 5) in the same manner as Example A.
  • Table 5 and Table 6 show the properties of the resulting biomass solid fuel B (Examples B-1 to B-4) obtained after the heating step.
  • Comparative Example B (WP) is also shown.
  • a binder is not used in Examples B-1 to B-4 and Comparative Example B, as is in Example A. Since the moisture contents after immersion in water are those after immersing more than 100 hours (168 hours in Example B), the moisture content in the solid fuel B is considered to have reached equilibrium.
  • Methods of measuring properties of the biomass solid fuel are the same as that described in the above Example A.
  • a ball mill grindability described in Table 6 was measured as follows.
  • the pulverizing time of each biomass solid fuel B was 20 minutes, and 150 ⁇ m sieve-passed weight ratio after 20 minutes was determined as pulverizing point.
  • measuring was carried out by using a ball mill conforming to JIS M4002, wherein into a cylindrical container having an inner diameter of 305 mm ⁇ axial length of 305 mm, normal grade ball bearings as defined in JIS B1501 ( ⁇ 36.5 mm ⁇ 43 balls, ⁇ 30.2 mm ⁇ 67 balls, ⁇ 24.4 mm ⁇ 10 balls, ⁇ 19.1 mm ⁇ 71 balls and ⁇ 15.9 mm ⁇ 94 balls) was charged and the container was rotated at a speed of 70 rpm. The higher value indicates that the grindability is improved. It was confirmed that with the increase in the heating temperature, pulverizing point increased.
  • Comparative Example B disintegrated immediately after immersion in water.
  • the bonding or adhesion between pulverized biomass particles are maintained even after immersion in water (168 hours), and they did not disintegrate.
  • the grindability is improved compared with Comparative Example B, and also COD is reduced.
  • the biomass solid fuel of Example B-3 is particularly excellent, and from the viewpoint of yield, the biomass solid fuels of Examples B-2 and B-3 showed particularly excellent physical properties.
  • Example B-2 has excellent water resistance and grindability based on the development of solid cross-linking, and is a fuel exhibiting reduced COD.
  • Example C-1 to C-4 PBT
  • the ball mill grindability was measured in the same manner as in the above example B.
  • Table 5 and Table 6 show the properties of the resulting biomass solid fuel C obtained after the heating step. Similar to Example B, since the moisture contents after immersion in water are those after immersing more than 100 hours (168 hours in Example C), the moisture content is considered to have reached equilibrium. Similarly, the properties of Comparative Example C (WP) is also shown. A binder is not used in Examples C-1 to C-4 and Comparative Example C.
  • Comparative Example C disintegrated immediately after immersion in water.
  • Examples C-1 to C-4 the bonding or adhesion between pulverized biomass particles were maintained even after immersion in water, and they did not disintegrate, indicating that water resistance is improved.
  • improvement of grindability and reduction of COD are indicated.
  • Examples C-2, C-3 and C-4 are excellent, and from the viewpoint of thermal yield, Examples C-1, C-2 and C-3 are excellent.
  • HGI of Example C-1 is lower than that of Comparative Example C, this is believed to be due to variations in raw materials and measurement errors, and therefore, Example C-1 is presumed to have HGI value equal to or more than at least Comparative Example C.
  • Example D-1 to D-4 PBT
  • Table 5 and Table 6 show the properties of the resulting biomass solid fuel D obtained after the heating step. Since the moisture contents after immersion in water are those after immersing more than 100 hours (168 hours in Example D), the moisture content is considered to have reached equilibrium. Similarly, the properties of Comparative Example D (WP) is also shown. A binder is not used in Examples D-1 to D-4 and Comparative Example D.
  • Comparative Example D disintegrated immediately after immersion in water.
  • Examples D-1 to D-4 the bonding or adhesion between pulverized biomass particles were maintained even after immersion in water, and they did not disintegrate, indicating that water resistance is improved.
  • improvement of grindability and reduction of COD are indicated.
  • Examples D-2, D-3 and D-4 are excellent, and from the viewpoint of thermal yield, Examples D-1, D-2 and D-3 showed particularly excellent physical properties.
  • Example E-1 to E-3 PBT
  • Table 5 and Table 6 show the properties of the resulting biomass solid fuel E obtained after the heating step. Since the moisture contents after immersion in water are those after immersing more than 100 hours (168 hours in Example E), the moisture content is considered to have reached equilibrium. Similarly, the properties of Comparative Example E (WP) is also shown. A binder is not used in Examples E-1 to E-3 and Comparative Example E.
  • Example E measurement of pH was carried out by immersing solid fuels with the solid-liquid ratio of 1:13.
  • the immersion time of Comparative Example E in Table 6 is a time when pH was measured, namely, it means that pH was measured at 96 hours after the solid fuel of Comparative example E was immersed.
  • Example E Comparative Example E disintegrated immediately after immersion in water. However, in Examples E-1 to E-3, the bonding or adhesion between pulverized biomass particles are maintained, and they did not disintegrate, showing water resistance. From the viewpoint of water resistance (moisture content after immersion), Examples E-2 and E-3 are excellent, and from the viewpoint of thermal yield, Examples E-1 and E-2 are excellent.
  • Example E it is estimated that the solid-cross-linking described above is formed also in PBT heated at 240 to 270° C., and therefore water resistance, COD, and grindability and the like are considered excellent. While thermal yield of Example E-1 exceeds 100%, this was caused by variations in raw materials and measurement errors.
  • Example F Except for using acacia bark as a biomass raw material, the biomass raw material is heated to target temperatures (heating temperatures described in Table 5) in the same manner as Example E (Examples F-1 to F-4: PBT).
  • Table 5 and Table 6 show the properties of the resulting biomass solid fuel F obtained after the heating step. Since the moisture contents after immersion in water are those after immersing more than 100 hours (168 hours in Example F), the moisture content is considered to have reached equilibrium. Similarly, the properties of Comparative Example F (WP) is also shown. A binder is not used in Examples F-1 to F-4 and Comparative Example F.
  • measurement of pH was carried out by immersing solid fuels with the solid-liquid ratio of 1:13.
  • the immersion time of Comparative Example F in Table 6 is a time when pH was measured, namely, it means that pH was measured at 96 hours after the solid fuel of Comparative example F was immersed.
  • Comparative Example F disintegrated one hour after immersion in water. However, in Examples F-1 to F-4, the bonding or adhesion between pulverized biomass particles are maintained, and they did not disintegrate, showing water resistance. From the viewpoints of COD and water resistance (moisture content after immersion), Examples F-2, F-3 and F-4 are excellent, and from the viewpoint of thermal yield, Examples F-1, F-2 and F-3 are excellent.
  • Example G-1 to G-4 PBT
  • Table 5 and Table 6 show the properties of the resulting biomass solid fuel G obtained after the heating step. Since the moisture contents after immersion in water are those after immersing more than 100 hours (144 hours in Example G), the moisture content is considered to have reached equilibrium. Similarly, the properties of Comparative Example F (WP) is also shown. A binder is not used in Examples G-1 to G-4 and Comparative Example G.
  • Comparative Example G disintegrated immediately after immersion in water. However, in Examples G-1 to G-4, the bonding or adhesion between pulverized biomass particles are maintained, and they did not disintegrate, showing water resistance. From the viewpoints of COD and water resistance (moisture content after immersion), Examples G-2, G-3 and G-4 are excellent, and from the viewpoint of thermal yield, Examples G-1, G-2 and G-3 are excellent. While thermal yield of Example G-2 exceeds 100%, this was caused by variations in raw materials and measurement errors.
  • Example H-1 to H-4 PBT
  • the ball mill grindability was measured in the same manner as in the above example B.
  • Table 5 and Table 6 show the properties of the resulting biomass solid fuel H obtained after the heating step. Since the moisture contents after immersion in water are those after immersing more than 100 hours (168 hours in Example H), the moisture content is considered to have reached equilibrium. Similarly, the properties of Comparative Example H (WP) is also shown. A binder is not used in Examples H-1 to H-4 and Comparative Example H.
  • the immersion time of Comparative Example H in Table 6 is a time when pH was measured, namely, it means that pH was measured at 24 hours after the solid fuel of Comparative example H was immersed.
  • Comparative Example H disintegrated three hours after immersion in water. However, in Examples H-1 to H-4, the bonding or adhesion between pulverized biomass particles are maintained, and they did not disintegrate, showing water resistance. From the viewpoints of COD, pH (slightly low) and water resistance (moisture content after immersion), Examples H-2, H-3 and H-4 are excellent, and from the viewpoint of thermal yield, Examples H-1, H-2 and H-3 are excellent.
  • Example I-1 to I-4 PBT
  • Table 5 and Table 6 show the properties of the resulting biomass solid fuel I obtained after the heating step. Since the moisture contents after immersion in water are those after immersing more than 100 hours (168 hours in Example I), the moisture content is considered to have reached equilibrium. Similarly, the properties of Comparative Example I (WP) is also shown. A binder is not used in Examples I-1 to I-4 and Comparative Example I.
  • Example I-3 The mechanical durability before and after immersion in water for Example I-3 that had been heated at 270° C. and Example I-4 that had been heated at 300° C. was measured by the following method.
  • 50 g of sample was filled in a 1,000 cc container made of polypropylene, and rotated at 60 rpm for 30 minutes (1,800 rotations in total) using Mazemazeman (trade mark) SKH-15DT manufactured by MISUGI LTD.
  • the sample after rotation treatment was sieved by a sieve having a circular hole diameter of 3.15 mm, and mechanical durability (DU) was calculated by the following equation:
  • m0 is a sample weight before rotation treatment
  • m1 is a sieve-on weight of sample after the rotation treatment.
  • Comparative Example I disintegrated immediately after immersion in water. However, in Examples I-1 to I-4, the bonding or adhesion between pulverized biomass particles are maintained, and they did not disintegrate, showing water resistance. From the viewpoints of COD and water resistance (moisture content after immersion), Examples I-2, I-3 and I-4 are excellent, and from the viewpoint of thermal yield, Examples I-1, I-2 and I-3 are excellent.
  • Example J-1 and J-2 PBT
  • Table 5 and Table 6 show the properties of the resulting biomass solid fuel J obtained after the heating step. Since the moisture contents after immersion in water are those after immersing more than 100 hours (168 hours in Example J), the moisture content is considered to have reached equilibrium. Similarly, the properties of Comparative Example J (WP) is also shown. A binder is not used in Examples J-1 and J-2 and Comparative Example J.
  • Comparative Example J disintegrated immediately after immersion in water. However, in Examples J-1 and J-2, the bonding or adhesion between pulverized biomass particles are maintained, and they did not disintegrate, showing water resistance. Excellent results were obtained also for COD.
  • Example K Except for using rubber tree as a biomass raw material, and except for using a tubular furnace having ⁇ 70 mm as a heating apparatus, the biomass raw material was heated to target temperatures (heating temperatures described in Table 5) in the same manner as Example A (Example K-1). Table 5 and Table 6 show the properties of the resulting biomass solid fuel K obtained after the heating step. Similarly, the properties of Comparative Example K (WP) is also shown. A binder is not used in Examples and Comparative Example.
  • Comparative Example K is expected to disintegrate by immersion in water as the other Comparative Examples. On the other hand, it is expected that Example K-1 does not disintegrate even by immersion in water due to the above solid cross-linking, and the improvement of grindability, reduction of COD and the like will be obtained. While Example K-1 was heated at 270° C., the same effect is expected to the heating temperature of 230 to 270° C. in the same manner as described above.
  • the pellet length of the solid fuels of Examples A-1 and A-3 before and after immersion in water was measured.
  • ten pellets before the immersion was chosen and their length was measure by an electronic caliper (manufactured by Mitutoyo: CD-15CX, repeating precision is 0.01 mm and the second decimal place was rounded.) and the length of the same pellets after 72 hours immersion in water were measured again by electronic caliper.
  • the length up to the most distal end portion was measured. Table 7 shows the measurement results. As shown in Table 7, the pellet length of Example A-1 increased by 4.6% in average, and Example A-3 increased by 0.2% in average.
  • pellet diameter of the solid fuels of Examples A-1 to A-6 before and after immersion in water was measured by the same electronic caliper and the same measurement method as for Table 7.
  • Table 8 shows the measurement results.
  • the measured value of the pellet diameter is an average values of ten samples randomly selected respectively from Examples A-1 to A-6.
  • Table 7 and Table 8 indicate that higher temperature in the heating step provides lower expansion ratio. Expansion is assumed to be suppressed by the formation of solid-linking due to heating. While the diameter expansion ratio of Table 8 is larger than the length expansion ratio of Table 7, this is considered because the immersion time is longer in Table 7, and also because Example A is in a pellet form which has been compacted mainly in the radial direction and therefore the expansion in the radial direction becomes large. It is noted that in Table 8, the diameter expansion ratio remains 10% or less even in Example A-1 which has the largest expansion ratio. In example A, the diameter and length expansion ratios are preferably 10% or less, and more preferably 7% or less. The volume expansion ratio is preferably 133% or less, and more preferably 123% or less.
  • Example B is in a pellet form, and thus the diameter expansion ratio was calculated based on equation (2) using the pellet diameter before immersion (initial dimensions in Table 6) and the pellet diameter after immersion (dimension after immersion in Table 6), and the result is 15% or less (note that equation (2) is used for the calculation of diameter expansion ratios for Example B thereafter). Since the length expansion ratio ⁇ diameter expansion ratio can be estimated for the pellet form as in Example A, the length expansion ratio in Example B can be assumed up to 15% or less. Then, the volume expansion ratio is calculated as 152% or less (the volume after immersion relative to the volume 100% before immersion; and the same applies to the following Examples C and thereafter). In Example B, the diameter expansion ratio is preferably 20% or less, and more preferably 10% or less. The volume expansion ratio is preferably 173% or less, and more preferably 133% or less.
  • Example C is also in a pellet form, the diameter expansion ratio before and after the immersion is 7.2% or less, and the length expansion ratio is assumed 7.2% at largest; and thus the volume expansion ratio is 123% or less (the volume expansion ratios of pellets in the following Examples will be calculated in the same manner).
  • the diameter expansion ratio is preferably 13% or less, and more preferably 7% or less.
  • the volume expansion ratio is preferably 144% or less, and more preferably 123% or less.
  • Example D in a pellet form, the diameter expansion ratio before and after the immersion is 8.8%, and the volume expansion ratio based thereon is 129% or less.
  • the diameter expansion ratio is preferably 10% or less, and more preferably 8% or less.
  • the volume expansion ratio is preferably 133% or less, and more preferably 126% or less.
  • Example E is in a tablet shape, the diameter ( ⁇ ) expansion ratio is 2.5% or less, the height (H) expansion ratio is 40% or less, and the volume expansion ratio is 147% or less.
  • the diameter expansion ratio is preferably 5% or less, and more preferably 2.3% or less.
  • the height expansion ratio is preferably 50% or less, more preferably 20% or less.
  • the volume expansion ratio is preferably 165% or less, and more preferably 126% or less.
  • Example F in a tablet shape, the diameter expansion ratio is 4.0% or less, the height expansion ratio is 15% or less, and the volume expansion ratio is 124% or less.
  • the diameter expansion ratio is preferably 5% or less, more preferably 3% or less.
  • the height expansion ratio is preferably 40% or less, and more preferably 10% or less.
  • the volume expansion ratio is preferably 154% or less, and more preferably to 117% or less.
  • Example G in a pellet form, the diameter expansion ratio before and after the immersion is 8.8% or less, and the volume expansion ratio based thereon is 129% or less.
  • the diameter expansion ratio is preferably 10% or less, and more preferably 8% or less.
  • the volume expansion ratio is preferably 133% or less, and more preferably 126% or less.
  • Example H in a pellet form, the diameter expansion ratio before and after the immersion is 6.9% or less, and the volume expansion ratio based thereon is 122% or less.
  • the diameter expansion ratio is preferably 10% or less, and more preferably 7% or less.
  • the volume expansion ratio is preferably 133% or less, and more preferably 123% or less.
  • Example I in a pellet form, the diameter expansion ratio before and after the immersion is 4.1% or less, and the volume expansion ratio based thereon is 113% or less.
  • the diameter expansion ratio is preferably 10% or less, and more preferably 5% or less.
  • the volume expansion ratio is preferably 133% or less, and more preferably 116% or less.
  • Example J in a pellet form, the diameter expansion ratio before and after the immersion is 5.4% or less, and the volume expansion ratio based thereon is 117% or less.
  • the diameter expansion ratio is preferably 20% or less, and more preferably 10% or less.
  • the volume expansion ratio is preferably 173% or less, and more preferably 133% or less.
  • the length (including diameter and height) expansion ratio before and after the immersion is preferably 40% or less for each case, and the volume expansion ratio is preferably about 275% or less. It is further more preferred that the diameter and length expansion ratios are 30% or less and the volume expansion ratio is about 220% or less. It is yet further more preferred that the diameter and length expansion ratios are 20% or less and the volume expansion ratio is about 173% or less. It is yet further more preferred that the diameter and length expansion ratios are 10% or less and the volume expansion ratio is about 133% or less. If the expansion ratio after immersion in water is within a certain range as above, the biomass solid fuel (PBT) does not disintegrate even by immersion, showing that it has water resistance.

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WO2020184698A1 (ja) * 2019-03-13 2020-09-17 日本製紙株式会社 固体燃料の製造方法
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WO2020203163A1 (ja) * 2019-03-29 2020-10-08 日本製紙株式会社 固体燃料の製造方法
JP2020186362A (ja) 2019-05-13 2020-11-19 バイ ホン メイＢａｉ， Ｈｏｎｇ Ｍｅｉ 固体バイオマス燃料の製造方法
CN110375516A (zh) * 2019-07-17 2019-10-25 安徽鼎梁科技能源股份有限公司 一种生物质颗粒冷却器
WO2021024001A1 (en) 2019-08-08 2021-02-11 Hamer, Christopher Process for producing solid biomass fuel
GB2599728A (en) 2020-10-12 2022-04-13 Mei Bai Hong Process for producing solid biomass fuel
GB202117376D0 (en) 2021-12-01 2022-01-12 Bai hong mei Process for producing solid biomass fuel

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